Process for the production of hydrogen



Patented Sept.'1 2-,1 933 ing equation:

r CO2 is formed inaddition to the CO UNITED P- T rnoosssroa- THE PRODUCTION OF 1 HYDROGEN V "Fritz Hansg irg, Vienna, Austria, assignor to American Magnesium. Metals Corporation,

Pittsburgh, Pa., a corporation of Delaware I No Drawing? Original applicationMay '29, 1930,

Serial "No. 457,500, now Patent No. 1,836,919, 7 and in] Austria June.18,- 1929. Divided and this application No. 517,114

February 19, 1931. Serial V 9 Claims. (c1. 23-212.)

' This invention relates to a process for the production oi hydrogen from steam and more particularly to su'ch'a process involving the use of an improved catalyst. ,This application is andivision of my, application Serial Number 457,500, filed May 29, 1930 (patent December 15,'1931). V i 1 The decomposition of water by means of incandescent carbon, as in the preparation of water gastakes place according to the follownumber 1,836,9 1 9 issued At lower temperatures below 1,000 degrees C,

V inaccordoxide, and, in addition, requiresa much smaller expenditure of heat, it wouldbe of advantage to prepare hydrogen from steam in accordance with that equation. The gaseous mixture obtained at the lower temperature range would also be most suited for the commercial recovery of hydrogen gas-sincethe removal of carbon dioxide is easier 7 in practice than is the elimination of carbon monoxide.

tical working due to its progressive decrease with lower temperatures. 1 i

, Attemptshave been frequently made to over come this inconvenience in orderto make possible thedirect recovery'of hydrogen, almost free from carbon monoxide by conducting theprocess in accordance with Equation II. order to increase the velocity of the reaction, it has been proposed, inter alia, to employ, as catalystsghydratesor carbonates of the alkalis, or the corresponding Water-soluble compounds of the alkaline earths. According to these'known processes materials containing carbon and impregnated with'the said water-soluble compounds were to be exposed, in an incandescent state, to the action 'ofordinary or super-heated steam.

a separate operation.

At the temperatures atwhich the; equilibriumdefined in E uationII takes place, i the reaction velocity is much" too slow for prac- The proposals advanced in thisdirection; however, did not prove successful, and consequently,

for the commercial recovery of -hydrogen,- the water gas processwas allowed to proceed at high temperature-the carbon monoxide being then removed from the resulting gaseous 'smixture in The present invention solves, inthe first place,

theproblem of the direct production of a mixture 'ofhydrogen and carbon dioxide,low in, or, free from, carbon monoxide, by the action of steam on carbon (or solid substances containing carbon), in the presence of additions which accelerate the reaction, and under conditions substantially approximating Equation II of the water gas process.

According to the invention, the process is cone 1 ducted withthe employmentof magnesia, mag: nesium carbonateor magnesium hydroxide,- as V catalysts, at a temperaturejwhioh,though above The invention is basedupon the fact that the mono-PC1025 c r are of decisive importance for the production of the decomposition temperature of magnesium carbonate, does not substantially exceed. 750 C. 7'0

'equilibria associated with thereaction I hydrogen free from ,carbon' monoxide, From1' this point of, View, the temperature of 500?, C.

is the most favorable temperature for thereaction, injthat, at this temperature, the equilibrium is practically completelydisplaced, in favor of carbon dioxide. Above 500 0., CO2 in the presence of C,,is reconverted into CO to an increasing .extentjas thetemperature rises, so that, for the formation of. a gaseous mixture low' in carbon I monoxide, the rangeof temperature above 750? C. isnot'longer to be considered, Belowfl700- 750 c., however,"the reaction velocity of the hy} drogen' process. is; already retarded tosuch an extent: that the reaction cannot be carried out on a technical scale. Theproblem therefore arose, of finding an eiiective and insensitivecontact ,masswhich will enable the reaction velocity of :the formation of hydrogento be sufficientlyinw creased in the range of temperature below 750 C. A mixture of carbon with magnesium care 'bonate has been found admirably suited for the purpose, This is based'on the relatively low decomposition temperature oi magnesium carbon- 7 ate, which can be reduced to even below-500 C. by dilutingthe gas phase-with steam, and thereby lowering the partial pressure of the carbon dioxide.

At 500 C. the reaction M co ezivi oq-co occurs to form an equilibrium, when theamounts of steam: employed correspond to the stoichioslightly exceed those proportions] Magnesium carbonate therefore has the capacity of rapidly absorbing, and again parting with, carbon ldi oxide in the hydrogen process conducted. in accordance with Equation II, at the'optimum-tem-fi' perature suitable for reliably preventing the-for mation of carbon monoxide. This'is not the case, either with the alkali carbonates or calcium v to free water gas from carbon monoxide by sub-- carbonate. According to the invention, the performance of the hydrogen process with the user; of magnesium carbonate as catalyst, at temperatureswhich do not substantially .exceed 500 0.,

enables hydrogen practically free from'carbon monoxide, to be obtained directly.

' If, for example, wood charcoal be mixedwith magnesium carbonate, in the proportions of 100 partsaby weight of .charcoalz-tou5-25 partsv by weight of magnesium carbonate, and such mixture be treated, 'at about 500 with the stoichiometrical amount of steam (corresponding -to 2 molecules of H20 to 1 molof C), the *react'ion proceeds in practical accordance'with Equation II and with quite sufiici'ent velocity. The

process is also of importance for the production of mixtures of hydrogen and carb n dioxide. However, since, as is known," the carbondioxide can beeasily'separated from thismixture, the

'methodfor the recovery of pure hydrogen.

" Of course, magnesium oxide or hydrom'de,

. which are immediately converted into magnesium carbonate, can be introduced into the reaction in placeof magnesium "carbonate. The process canalso-be' carried'out with crude materials which-contain magnesium oxide or hydroxide in Fsufhcient' amOunt. The catalyst remains, unalteredin composition and active', without regeneration, so'that only the g'asified carbon has to'be replaced. Since the course'of; the reaction for the formation of hydrogen in accordancewith Equation II is slightly endothermic, the reaction temperature'of" approximately 500 'C. oanbe maintained by the application of a very small amount of heat.

. 3 J Example An intimate mixture of wood charcoal and calcined magnesiteand containing, for example, 1

part by weight of magnesium oxidefor every 4 parts by weight of charcoal, is allowed'tc descend' through an externally heated shaft furnace inwhich the contact mass is maintained at about 500 C. Steam is passed in counter flow, through the descending charge. The contact mass, low

in charcoaLissuingat the lower end of the shaft is again mixed .with suflicient added charcoal to restore the desired m'agnesiumoxideecharcoal ratio, and the resulting mixture is returned into the topv of the shaft furnace, thus'permittinga cyclic operation of, the-process. In this manner,

stance. can be converted per hour;

furnace, operated in a similar manner. 'If the carbon dioxide be removedfrom the resulting, mixtures with hydrogen (free from cartemperatures occurring in the. present process,

ing reacting steam with an intimate mixture of ing. reacting steam with'a mixture comprising with water under pressure to remove the carbon bon monoxide) i in the known manner,.for example by washing with water under pressure,

' this very: simple process furnishes perfectly pure hydrogen'ina direct manner, that is, without any chemical purification being required.

The value, as an improvement, of thepresent process which, by the employment of .a very cheap and insensitive contact mass, solves the 7 problem of the direct gasification of a carbonac'eous material such as charcoal, in the presence sequent oxidation with the aid of expensive and sensitive catalysts.

, The terman oxygen compound of magnesium as used in. the appended claims is intended to include only magnesium oxide, substances yielding magnesium oxide on being heated up to the and mixtures of magnesium oxide with substances yielding magnesium oxide under the temperature conditions of the present process, such as more particularly magnesium Carbonate,

What is claimed is: I a

1.. The process of obtaining hydrogen,iinclud ing'react'ing steam with an intimate mixture of a solid carbonaceous material and a catalyst comprising" an oxygen compound of magnesium.

2. The process of obtaining hydrogen, including reacting steam with an intimate mixture of a solid carbonaceous material and a catalyst comprising an oxygen compound of magnesium at a temperature of substantially 500 C.

3. The processor obtaining hydrogen, including reacting steam with .a mixture of charcoal and magnesium carbonate. 7

i. The process of obtaining hydrogen, includingreacting steam with a mixture comprising 100 parts of charcoaland 5 to 25parts of mag- 5. The process of obtaining hydrogen, includ .ing reacting steam with an intimate mixture of a solid carbonaceous material and a catalyst comprising magnesium oxide;

a solid carbonaceous material and a catalyst comprising magnesium hydroxide.

7.=The process of obtaining hydrogen, includ- 100, partsof charcoal and 5 to 25 parts of magnesium corbonate, the steam being present in the stoichiometrical amount of two molecules of R20 to 1 molecule of carbon. 7

8. The process of obtaining hydrogen, including reacting'steam with a mixture of a carbonaceous material and an oxygen compound of magnesiumat a temperature not substantially exceeding 750 (3., whereby to form hydrogen and carbon dioxide according to the equation:

C+2 II 20=CO2+2H218.0 kg. cal.; and washing the so-formed reaction products dioxide.

- 9, The process-of obtaining hydrogen, including passing steam and a mixture of a carbona- .ceous; material and an oxymagnesium compound of the group consisting of magnesium carbonate, magnesium oxide, magnesium hydroxide.

carbon dioxide according to equation:

i n couhter-current through {reaction chamber maintained at a temperetureijnot substantially exceeding 500 C., whereby to form'hydrogen and c+2mo=oo2+2m 1al o kg. ca1.;" withdrawing the evolved ggseou'sfm'ixture end 7 mixturetothe process.

' material, and returning the replenished reaction FRITZ HANSGI RGr 

